JP2015097208A - Organic electronic panel and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for removing an electrode lead in a small space without deteriorating sealing performance while the conductivity and the adhesiveness thereof are sufficiently maintained, in an organic electronic panel using a flexible substrate.SOLUTION: In an organic electronic panel, an organic electronic element configured so that a pair of electrodes 2, 4 are provided on a supporting substrate 1, and an organic compound layer 3 containing a function layer comprising at least an organic compound is sandwiched by the pair of electrodes, is hermetically sealed by a sealing member 5 covering the organic electronic element, between the supporting substrate and the sealing member while the electrodes and the organic compound layer are held. A joint portion between a pulling portion 2a of each electrode and an electrode lead 7 connected to an outside drive circuit is disposed within an area covered and hermetically sealed by the sealing member, and the electrode lead is removed from the hermetically sealed area.

Description

  The present invention relates to a method for sealing an organic electronic element, and in particular, relates to an organic electroluminescence element (organic EL element), a connection between an electrode of an organic photoelectric conversion element and an electrode lead (flexible printed circuit board).

  In recent years, organic electronics elements are elements that perform electrical operations using organic substances, and are expected to exhibit features such as energy saving, low cost, and flexibility. As a technology to replace conventional inorganic semiconductors mainly composed of silicon. Attention has been paid.

  These organic electronics elements emit light, control current and voltage, or generate electricity by charging light or charge by passing an electric current through an electrode through a very thin film of organic matter. It is an element to do.

  An electroluminescence element (hereinafter also referred to as an EL element), which is one of these, has attracted attention in display applications and illumination applications.

  However, the organic EL element is vulnerable to moisture and oxygen, and it is necessary to prevent this from moisture and oxygen using a sealing member such as a sealing can and a sealing plate.

  The organic photoelectric conversion element is an organic electronic element having a structure similar to that of the organic electroluminescence element, but the light emitting layer of the organic electroluminescence element is a photoelectric conversion layer made of a thin film of an organic compound, and this is sandwiched between electrodes. It is an element which has the structure mentioned above and generates electric power when irradiated with light. Therefore, if a thin-film organic photoelectric conversion element is used as a solar cell, it is easy to reduce the size and weight, and the output is relatively stable even in low-light and high-temperature environments compared to existing inorganic semiconductor solar cells. The solar cell can be obtained.

  In the organic photoelectric conversion element, similarly to the organic EL element, carrier traps are formed in the power generation layer (photoelectric conversion layer) due to the influence of moisture, oxygen, etc., thereby preventing the collection of carriers generated by charge separation. End up. As a result, this not only reduces the power generation efficiency, but also affects the device life. Therefore, in the organic photoelectric conversion element, it is similarly studied to secure performance by using a sealing material having barrier performance against gas components such as moisture and oxygen (for example, Patent Document 1). ).

  On the other hand, in order to supply electric power to the organic EL element or to extract electric power from the organic photoelectric conversion element, it is necessary to connect an electrode lead (flexible printed circuit board). However, in these elements, when an electrode lead is connected to the outside of the sealing member, the electrode member must be formed to extend to the outside of the sealing member, so that an extra electrode space is taken and a space is taken up. In particular, in the case of a transparent conductive film such as ITO used as a transparent electrode, there is a problem that, when the area or the length of the conductive film is extended to the outside, a voltage drop is caused due to its electric resistance.

  In Patent Document 2 (Japanese Patent Application Laid-Open No. 2001-215881), when a sealing can is used for sealing, the electrode lead connection portion and the sealing can are overlapped, that is, the electrode on the substrate and the flexible printed circuit board. It is described that space is saved by sandwiching the connecting portion between the glass substrate and the sealing substrate. However, with this method, it has been found that when a flexible substrate is used, it is difficult to cope with sealing, and there is a problem in sealing performance when stored in a high temperature and high humidity state.

JP 2004-165512 A JP 2001-215881 A

  An object of the present invention is a method for taking out an electrode lead in a space-saving manner without deteriorating sealing performance while maintaining sufficient conductivity and adhesiveness in sealing an organic electronic element using a flexible substrate. Is to provide.

  The above object of the present invention is achieved by the following means.

1. An organic electronics element having a structure in which an organic compound layer including a functional layer made of at least an organic compound is sandwiched between a pair of electrodes on a support substrate, and a sealing member covering the organic electronics element between the support substrate and An organic electronics panel sandwiched between an electrode and an organic compound layer and closely sealed,
The joint between the electrode lead-out portion and the electrode lead connected to the external drive circuit is in the close-sealed region covered by the sealing member, and the electrode lead extends from the close-sealed region. Taken out,
The organic electronics panel has a pair of electrodes and a functional layer made of at least an organic compound therebetween in one direction on the support substrate in a plan view. ) A region where the one electrode and the functional layer made of the organic compound overlap, (3) a region where the one electrode and the functional layer made of the organic compound overlap the other electrode, and (4) a functional layer made of the organic compound. And the region where the other electrode overlaps, (5) the region where only the other electrode is disposed,
In addition, the joint between the electrode lead-out portion and the electrode lead connected to the external drive circuit is in the same direction as the arrangement of the regions (1) to (5), and (1) and (5) Located on the outside,
Organic electronics panel characterized by that.

  2. 2. The organic electronics panel as described in 1 above, wherein the functional layer is a light emitting layer, and the organic electronics element is an organic electroluminescence element.

  3. 2. The organic electronics panel according to 1 above, wherein the functional layer is a photoelectric conversion layer and the organic electronics element is an organic photoelectric conversion element.

  4). 4. The organic electronics panel according to any one of items 1 to 3, wherein the support substrate is a flexible resin substrate.

5). An organic electronic element having a structure in which an organic compound layer including a functional layer made of at least an organic compound is sandwiched between a pair of electrodes on a supporting substrate, and the electrode and the organic compound between the supporting substrate by a sealing member A method for producing an organic electronics panel in which layers are sandwiched and closely sealed,
A joint portion between the electrode lead-out portion and an electrode lead connected to an external drive circuit is adhered by a conductive adhesive, and the sealing member covers the joint portion and tightly seals the organic electronics element. Stop,
The organic electronics panel has a pair of electrodes and a functional layer made of at least an organic compound therebetween in one direction on the support substrate in a plan view. ) A region where the one electrode and the functional layer made of the organic compound overlap, (3) a region where the one electrode and the functional layer made of the organic compound overlap the other electrode, and (4) a functional layer made of the organic compound. And the region where the other electrode overlaps, (5) the region where only the other electrode is disposed,
In addition, the joint between the electrode lead-out portion and the electrode lead connected to the external drive circuit is in the same direction as the arrangement of the regions (1) to (5), and (1) and (5) Located on the outside,
A method for producing an organic electronics panel.

  6). 6. The method for producing an organic electronics panel as described in 5 above, wherein the functional layer is a light emitting layer and the organic electronics element is an organic electroluminescence element.

  7). 6. The method for producing an organic electronics panel as described in 5 above, wherein the functional layer is a photoelectric conversion layer, and the organic electronics element is an organic photoelectric conversion element.

  8). 8. The method of manufacturing an organic electronics panel according to any one of 5 to 7, wherein the support substrate is a flexible resin substrate.

  9. 6. The method for producing an organic electronics panel according to 5, wherein a temperature at the time of adhesion of the conductive adhesive is 140 ° C. or less.

  10. 6. The method of manufacturing an organic electronics panel according to 5, wherein heating is performed from both sides of the joint portion when the conductive adhesive is bonded.

11. 6. The method for producing an organic electronics panel according to 5 above,
A method for producing an organic electronics panel, wherein the conductive adhesive has a moisture content of 100 ppm or less, and the electrode lead has a moisture content of 100 ppm or less.

  According to the present invention, it has a solid sealing structure capable of sufficiently maintaining the connection between the electrode lead and the electrode, and the adhesiveness therefor, without deteriorating the performance of the organic electroluminescence (EL) element or the organic photoelectric conversion element. An organic electronics panel manufacturing method and an organic electronics panel from which electrode leads can be taken out are obtained.

FIG. 2 is a schematic cross-sectional configuration diagram of close-contact sealing of an organic electronics panel according to the present invention. It is a cross-sectional structure schematic diagram which shows the sealing structure of the conventional organic electronics panel. It is a schematic diagram shown about a tent-like failure. FIG. 3 is a schematic cross-sectional configuration diagram showing an embodiment of the manufacture of the organic electronics panel of the present invention. It is a cross-sectional structure schematic diagram which shows the sealing structure of the organic electronics panel created in the Example. It is a schematic perspective view which shows the external appearance of the sealing member (sealing can) used for the organic electronics panel of the comparative example. FIG. 2 is a schematic plan view of the close-contact sealing of the organic electronics panel according to the present invention. It is a schematic diagram of the method of the peeling test using a push pull gauge.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  The present inventors diligently studied to take out electrode leads in a space-saving manner while satisfying sealing performance in a flexible substrate.

  As a result, it can be seen that the electrode lead can be attached while maintaining sufficient sealing performance by taking out the electrode lead from the inside (inside) of the solid sealing using a close sealing (solid sealing) type sealing. It was.

  Furthermore, in the hollow method, it is difficult to manufacture unless the distance between the light emitting part of the organic EL or the power generating part of the organic photoelectric conversion element and the adhesive part of the hollow seal is set to some extent. Since the light emitting part of the organic EL or the power generation part of the organic photoelectric conversion element is sealed if the solid sealing is stopped, the electrode lead can be adhered in the vicinity of the light emitting part or the power generation part. Therefore, an electrode lead portion such as an electrode made of a transparent conductive film having a high resistance value or a wiring routed thereby can be shortened, and a driving voltage as an organic electroluminescence (EL) panel can be reduced, or an organic photoelectric conversion panel The voltage and the shape factor ff can be improved.

  Further, it has been found that such a configuration improves the operational stability of the element during long-term storage, in addition to saving space and sufficient sealing performance. The reason for this is not clear, but it is presumed that at least the electrode lead connecting portion is protected by the close-sealed inner region, so that the electrode connecting portion can be maintained well.

  A preferred embodiment of the present invention will be described below with reference to the drawings.

  First, the organic electronics panel will be described.

  FIG. 1 shows an organic material including a pair of electrodes formed on a supporting substrate and a functional layer such as at least a light emitting layer (in the case of an organic EL element) or a photoelectric conversion layer (in the case of a photoelectric conversion element) between them. It is the cross-sectional structure schematic diagram which showed the organic electronics panel which carried out contact | adherence sealing (solid sealing) with the organic electronics element which has the structure which pinched | interposed the compound layer, and the sealing member which covers this.

  In the figure, on a flexible resin substrate 1 which is a support substrate, for example, an anode 2 made of ITO as a first electrode, and further an organic compound layer 3 including a functional layer such as a light emitting layer is further formed thereon, for example, A cathode 4 which is a second electrode made of aluminum or the like is laminated to form an organic electronics element which is an organic EL element or an organic photoelectric conversion element.

  The resin substrate 1 on which the organic electronics element is formed is tightly sealed by a sealing member 5. That is, the sealing member 5 is in close contact with the organic electronics element and the resin substrate by the sealing adhesive 6 and covers the entire surface to seal and isolate the organic electronics element from the external space (adhesion sealing). ). Here, each electrode (only the anode is shown here) is electrically bonded to the electrode lead (flexible printed circuit board) 7 for connection with an external drive circuit formed on the flexible printed circuit board in the electrode lead-out portion 2a. The adhesive 8 is tightly bonded and bonded (connected), and the bonded portion is in the tightly sealed internal region and the bonded portion is also sealed and connected, and the electrode lead is connected from the tightly sealed region to the outside. It has been taken out.

  By the way, close-contact sealing is also called solid sealing, and all the gaps are covered with resin (sealing adhesive) so as not to leave a space between the substrate on which the organic electronics element is formed and the sealing member. Thus, an organic electronic element, that is, an organic compound layer is sealed.

  In FIG. 7, the sealing structure and its arrangement | positioning were shown with the plane structure schematic diagram about another form of the organic electronics panel which concerns on this invention.

  The arrangement of the anode 2 and its extraction electrode 2a, the conductive adhesive 8 and the electrode lead 7 on the substrate 1 is shown in plan view. The organic compound layer 3 and the cathode 4 are also shown, and the arrangement of the cathode side extraction electrode (ITO) 4a is also shown.

  The adhesive layer 6 for solid sealing is layered by, for example, coating on the configuration of this plan view, and further the sealing member 5 is overlaid so that the joint between the electrode lead and the extraction electrode is tightly sealed. It is sealed so as to be a stopped internal region (omitted in the figure).

  By taking these sealing methods, the entire electrode lead is fixed by the sealing adhesive, so that the electrode lead is fixed not only by the joint with the electrode lead-out part, but also by the sealing adhesive, Because the adhesion area can be increased, the electrode lead part is fixed as a whole rather than the method of attaching and fixing the electrode lead and electrode lead-out part by pressing the adhesion part between the electrode lead and the electrode lead-out part with a conventional sealing can, so there is no peeling or loosening Can be firmly fixed. In addition, the electrode lead-out portion does not have to be formed out of the sealing member, and the electrode area can be designed compactly. This is advantageous particularly in the case of an electrode using a transparent conductive film such as ITO. When the size of the transparent conductive film is increased and the wiring routed by the transparent electrode or the like is increased, the transparent conductive film generally has a large electric resistance value, so that the voltage drop is large and the drive voltage is likely to increase. Although there is a method of providing a metal layer such as nickel as a countermeasure against a voltage drop or the like, the process becomes complicated and the cost increases.

  A conventional sealing structure will be described with reference to FIG.

  Fig.2 (a) is a cross-sectional schematic diagram of the sealing structure using the sealing can described in Unexamined-Japanese-Patent No. 2001-215881 (patent document 1). When sealing using the sealing member (sealing can) 5, the connection part of the electrode lead 7 and the sealing member 5 are sealed by overlapping the electrode lead-out part 2a. That is, a space between the anode 2 (electrode lead portion 2a) on the substrate and the electrode lead 7 (flexible printed circuit board) is sandwiched between the substrate and the sealing member 5 (sealing can) to save space. The portion 2a and the electrode lead 7 are arranged. In the figure, an electrode lead 7 is bonded by a conductive adhesive 8 in a form sandwiched between a sealing member 5 (sealing can) and an electrode lead-out portion. The sealing member is bonded to the electrode lead 7 with a sealing adhesive 6. Since the sealing member (sealing can) has a hollow structure, the electrode lead is only pressed by the peripheral portion of the sealing can, and since it has a hollow structure, the adhesion portion with the electrode lead cannot be made too large. For this reason, the bonding area cannot be increased, and the resin substrate cannot be firmly fixed. Further, when a flexible material is used for the sealing member, the entire panel is further flexible, and therefore, peeling easily occurs when a shift stress or the like is generated. In addition, when stored in a high-temperature and high-humidity state, it easily peels off, causing a problem in sealing performance.

  In the present invention, it is preferable to use a flexible resin substrate as the support substrate (or sealing member). As shown in FIG. 3, a flexible material is used for the support substrate or the sealing member. Such a tent-like failure can also be prevented, whereby the adhesion of the electrode leads can be made stronger.

  When an electrode lead such as an FPC (flexible printed circuit board) is taken out from the inside of the seal using a member whose support substrate 1 'and the sealing member 5 are not flexible, a tent-like failure (T) in the vicinity of the electrode lead There was a problem that it was easy to do. If this occurs, the manufacturing yield will be reduced. For this reason, it is necessary to increase the thickness of the sealing adhesive 6, reduce the thickness of the electrode lead, or devise the shape. If such a thing is done, demerits, such as a sealing performance fall and cost increase, will arise.

  On the other hand, when a flexible material is used for the support substrate 1 ′ or the sealing member 5, the sealing member 5 follows an unevenness like an FPC installed on the substrate, so that the tent shape described above is used. (T) is less likely to occur. The thickness of the sealing adhesive 6 can also be reduced, and the sealing performance can be improved.

  In addition, the hollow structure is difficult to manufacture unless the distance between the light emitting portion of the organic EL element or the power generating portion of the organic photoelectric conversion element and the bonding portion between the sealing can and the electrode lead is limited, and the space is saved. Or although an electrode lead is arrange | positioned, an electrode area becomes large inevitably, or an electrode extraction part becomes long.

  As another example of the conventional sealing structure, another example in which the electrode lead portion 2a is formed outside the sealing member is shown in FIG.

  In this case, it is necessary to make the electrode lead-out portion 2a large for connection with an electrode lead, that is, a flexible printed circuit board, so that it is not possible to save further space. growing.

  2 and 3, only one electrode has been described. However, for the other electrode (cathode 4 in the figure), for example, the electrode lead is taken out from a direction not shown in FIGS. It is not shown here. The same can be said for the cathode.

  Therefore, in the present invention, the connection portion between the electrode lead portion and the electrode lead connecting the external drive circuit is in the region tightly sealed by the sealing member, and the electrode from the close (solid) sealing portion is By taking out the lead, space-saving and without impairing the performance of the organic electronics element, especially when a flexible resin substrate is used for the sealing member, it is an excellent sealing method that is strong against bending and displacement is there.

  Next, the manufacturing method of the organic electronics panel of this invention is demonstrated.

  FIG. 4 is a cross-sectional schematic diagram showing an embodiment of the manufacture of the organic electronics panel of the present invention focusing on the connection between the electrode lead and the electrode lead-out portion of the organic electronics element.

  First, an anode 2 made of ITO and an ITO lead electrode 2a for driving an organic electronics element are formed on a resin substrate 1, and, for example, a hole transport layer, a light emitting layer, an electron transport layer (not individually shown above), etc. The organic compound layer 3 and the cathode 4 constituting the organic electronic element composed of the above are sequentially laminated to form the organic electronic element on the resin substrate 1 as shown in FIG. 1 (FIG. 4A). Here, the anode 2 is formed so that the driving ITO lead electrode 2a is connected. These can be formed by forming ITO on the entire surface of the flexible resin substrate 1 by sputtering, vapor deposition or the like and then etching it into a desired pattern. Alternatively, a desired resist pattern can be formed in advance, and ITO can be deposited, and the resist pattern can be lifted off. Furthermore, ITO can be directly formed by sputtering, vapor deposition or the like using a metal mask or the like in which a desired pattern is opened.

  Further, the organic compound layer 3 and the cathode 4 may be patterned so as to form pixels in a matrix shape, or may be uniformly formed on the entire surface in applications such as illumination.

  The cathode 4 is also formed so as to be connected to the electrode lead (driving circuit or flexible printed board) although not shown in the drawing.

  Next, an anisotropic conductive film is used as the conductive adhesive 8 and is temporarily bonded to the ITO electrode lead-out portion 2 a on the resin substrate 1. Thereafter, the electrode lead 7 (flexible printed circuit board) and its joint are aligned and bonded together. This adhesion is preferably performed under the pressure bonding conditions of the anisotropic conductive film. Electrical connection can be achieved by thermocompression bonding for several seconds to several minutes at a pressure of 0.1 to 10 MPa and a temperature of about 80 to 180 ° C. using an anisotropic conductive film.

  However, the temperature at the time of adhesion of the conductive adhesive is preferably 140 ° C. or lower, and when the temperature is lower than this temperature, the conductivity is better and the drive voltage is less increased. The reason for this effect is not clear, but because the linear expansion coefficients of transparent electrodes such as members used for electrode leads, resin substrates, and ITO differ, stress occurs in each member when bonded at a temperature extremely different from room temperature. In addition, it is estimated that this leads to poor conduction immediately afterwards and an increase in resistance during long-term storage.

  In addition, when the lead electrode and the electrode lead using the conductive adhesive 8 are bonded, it is preferable because they are uniformly cured because they are heated from both sides of the support substrate and the sealing member.

  A heating means is not particularly selected, but a heat plate, an oven, or a laminator using a pressure roll may be used as long as pressure can be applied. Generally, an ACF crimping machine or a bonder is used.

  For example, it is preferable to heat and compress the sample stage using a commercially available ACF crimping machine. It is not necessary for both the electrode lead and the resin substrate side to be at the same temperature, but it may be within the above temperature range. By heating from both sides and reducing the temperature difference (temperature gradient) between the conductive adhesive and, for example, the substrate side, the conductive adhesive is hardened uniformly, bonding becomes stronger, and peeling is less likely to occur. Become.

  As an anisotropic conductive film, conductive particles, for example, metal nuclei themselves, such as gold, nickel, and silver (also, for example, resin nuclei plated with gold, etc.) are dispersed in a binder. Plastic resins and thermosetting resins are used, and among them, thermosetting resins, particularly those using epoxy resins are preferable. A conductive paste having a similar structure may be used. An anisotropic conductive film in which nickel fibers (fibrous) are oriented can be used as a filler.

  When the anisotropic conductive film is thermocompression bonded to the resin substrate, electrical connection in the thickness direction is taken by the conductive particles, and at the same time, mechanical bonding is taken by the binder resin. Examples of the binder resin include thermosetting resins such as epoxy resins and phenolic resins, and thermoplastic resins such as polyamideimide. From the viewpoint of resin fluidity, connection reliability, cost, pot life, and the like, film-like epoxy is used. Resins are preferred. Examples of the conductive particles include metal particles such as nickel, copper and silver, and composite particles in which the surface of plastic particles such as acrylic resin and styrene resin is coated with a metal plating film such as nickel and gold. In particular, in terms of connection reliability, composite particles in which the particles themselves are flexible and have a restorable plastic particle are coated with a metal plating film such as nickel or gold. The conductive particle diameter is usually 3 to 5 μm.

  As the conductive adhesive, in addition to an anisotropic conductive film, a fluid material such as a conductive paste, for example, a silver paste or the like may be used. It can also be formed by printing or the like using a conductive paste on the electrode lead portion.

  Although not shown in FIGS. 2 and 3, the lead electrode formed in the same manner for the cathode metal layer and the electrode lead such as a flexible printed board are similarly connected.

  The electrode lead 7 is connected to the driving circuit and is formed of a conductor. The electrode lead that can be used in the present invention is not particularly limited as long as it has a low resistance value and can be made into a thin film, and aluminum foil, rolled copper foil, silver foil, gold foil, and the like can be used. For example, a copper-clad polyimide film obtained by attaching a rolled copper foil or the like to an insulating polyimide film can be preferably used. Further, a flexible printed circuit board (FPC) on which a drive circuit is mounted by patterning or cutting a copper-clad polyimide film can be used.

  Moreover, it is preferable that the moisture content of the said conductive adhesive and the said electrode lead is 100 ppm or less at the time of adhesion | attachment. By suppressing the mixing of water below this level, the adhesion is strengthened, and at the same time, the water permeability of the cured film can be kept low by curing at a low water content.

  The moisture content may be measured by any method. For example, a volumetric moisture meter (Karl Fischer), an infrared moisture meter, a microwave transmission moisture meter, a heat-dry weight method, GC / MS, IR, DSC (Differential scanning calorimeter) and TDS (temperature programmed desorption analysis). Further, using a precision moisture meter AVM-3000 (Omnitech) or the like, moisture can be measured from a pressure increase caused by evaporation of moisture, and moisture content of a film or solid film can be measured.

  After joining the electrode lead and the electrode lead-out portion, next, close sealing (solid sealing) is performed. As the sealing member 5 (sealing substrate), for example, a 50 μm thick PET (polyethylene terephthalate) laminated with an aluminum foil (30 μm thick) is used. With this as a sealing member 5, a sealing adhesive 6 (for example, a thermosetting adhesive (epoxy adhesive)) is disposed in advance on the aluminum surface (or the resin substrate 1 or both surfaces facing the aluminum surface). Then, after aligning the resin substrate 1 and the sealing member 5, both are pressure-bonded (0.1 to 3 MPa), and are adhered and bonded (adhered) at a temperature of 80 to 180 ° C. )

  An ultraviolet curable resin can also be used for this joining (adhesion). When an ultraviolet curable resin is used, light irradiation is required, and the organic electronics element is damaged when irradiated with ultraviolet rays. Therefore, when using an ultraviolet curable resin, it is necessary to reduce the ultraviolet irradiation as much as possible. As the sealing adhesive, a thermosetting resin is preferably used. Various known materials such as epoxy resins, acrylic resins, and silicone resins can be used.

  In particular, it is preferable to use an epoxy thermosetting adhesive resin that is excellent in moisture resistance and water resistance and has little shrinkage during curing.

  FIG. 4B shows a state where the sealing adhesive 6 is disposed on the sealing member 5.

  The thermosetting resin (adhesive) is applied evenly along the aluminum surface, if possible, for example, using a dispenser to form the sealing member 5 (PET laminated with aluminum foil). Covering the joint portion between the lead portion and the electrode lead, for example, closely contacting and arranging on the resin substrate on which the organic electronics element is formed, pressure bonding (for example, pressure 0.5 MPa), and temporary bonding. At this time, take care not to leave any air (cavities) in it. A pressure roll or a press may be used. The temporarily bonded organic electronics panel is placed on, for example, a hot plate and heated (for example, at a temperature of 120 ° C. for 30 minutes) to thermally cure the thermosetting adhesive, thereby closely sealing the organic EL element and the organic electronics element. Stop (solid sealing) to create an organic electronics panel. Since the electrode lead portion and the electrode lead connected to the electrode lead portion are fixed between the sealing member and the element substrate by the cured sealing adhesive, the electrode lead portion and the flexible circuit board can be fixed sufficiently firmly. .

  The heating or pressure bonding time varies depending on the type, amount, and area of the adhesive, but temporary bonding is performed at a pressure of 0.1 to 3 MPa, and the thermosetting time is within a range of 5 seconds to 10 minutes at a temperature of 80 to 180 ° C. Just choose.

  The use of a heated crimping roll is preferred because it allows simultaneous crimping (temporary bonding) and heating, and eliminates internal voids at the same time.

  In addition, as a method for forming the adhesive layer, a dispenser, a coating method such as roll coating, spin coating, screen printing, or spray coating, or a printing method can be used depending on the material.

  FIG. 4C schematically shows a cross-sectional configuration diagram of the organic electronics panel after close-sealing.

  Solid sealing is a form in which there is no space between the sealing substrate and the organic EL element organic electronics element substrate as described above, and is covered with a cured resin, and has a sealing material adhesion structure, and the electrode lead is also in the sealing resin. The electrode lead is taken out from the fixed and solid (solid) sealed portion.

  Solid sealing is a solid sealing structure that can maintain sufficient adhesion (bonding) strength in the connection between the electrode lead and the electrode, and the electrode lead can be taken out without degrading the performance of the organic electronics element. It is preferable in the manufacturing method of an organic electronics panel.

  Further, the sealing has been described above, but the bonding (connection) of the electrode lead to the electrode lead portion using the conductive adhesive is temporarily bonded (for example, a pressure of 0.1 to 2 MPa), and then sealed. It may be performed at the same time when the stopper member is adhered, and the electrode lead and the sealing member can be adhered at a time.

  Next, other components used in the present invention will be described.

  In carrying out the present invention, the material of each component is not particularly limited. That is, in the support substrate, the sealing member, and the organic electronic element, various known materials can be used as the first electrode (anode), the organic compound layer, the second electrode (cathode), the anisotropic conductive film, the adhesive, and the like. .

  In the organic electronics panel of the present invention, as the support substrate, a resin (plastic) substrate having a sheet shape or a film shape can be used. In particular, transparent plastics such as polyester, polymethacrylate, and polycarbonate having high transparency to light emission are suitable.

Moreover, it is preferable to use the gas barrier film which laminated | stacked 1 nm-several hundred nm of gas barrier layers, such as aluminum oxide, a silicon oxide, and silicon nitride, on these resin substrates. The gas barrier layer can also be formed on both surfaces or one surface of the resin substrate by plasma CVD, sputtering, vapor deposition, or the like. As the resin substrate or film, the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ cm ³ / (m ² · 24 h · atm) or less, and it conforms to JIS K 7129-1992. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by the method is preferably 1 × 10 ⁻³ g / (m ² · 24 h) or less. .

In addition, examples of the sealing member include metals such as stainless steel, aluminum, and magnesium alloys, polyethylene terephthalate, polycarbonate, polystyrene, nylon, plastics such as polyvinyl chloride, and composites thereof, glass, and the like. In particular, in the case of a resin film, a layer in which a gas barrier layer such as aluminum, aluminum oxide, silicon oxide, or silicon nitride is laminated can be used in the same manner as the resin substrate. The gas barrier layer can be formed by sputtering, vapor deposition or the like on both surfaces or one surface of the sealing member before molding the sealing member, or may be formed on both surfaces or one surface of the sealing member after sealing by a similar method. . Also about this, oxygen permeability is 1 × 10 ⁻³ cm ³ / (m ² · 24 h · atm) or less, water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is 1 X10 ⁻³ g / (m ² · 24 h) or less is preferable.

  The sealing member may be a film laminated with a metal foil such as aluminum. As a method for laminating the polymer film on one side of the metal foil, a generally used laminating machine can be used. As the adhesive, polyurethane-based, polyester-based, epoxy-based, acrylic-based adhesives and the like can be used. You may use a hardening | curing agent together as needed. A hot melt lamination method, an extrusion lamination method and a coextrusion lamination method can also be used, but a dry lamination method is preferred.

  If the metal foil is formed by sputtering or vapor deposition, or is formed from a fluid electrode material such as a conductive paste, it is created by using a polymer film as a base material and forming the metal foil on this. Also good.

  Next, the organic EL element will be described.

<< Organic EL element >>
An organic EL element has a structure in which one or a plurality of organic compound layers are laminated between electrodes. For example, various organic compounds such as an anode layer / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode layer, etc. It has a configuration in which functional layers made of a compound are laminated as necessary. Most simply, it has a structure comprising an anode layer / a light emitting layer / a cathode layer.

  Examples of organic compound materials used for the hole injection / transport layer include phthalocyanine derivatives, heterocyclic azoles, aromatic tertiary amines, polyvinyl carbazole, polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT: PSS), and the like. A polymer material such as a conductive polymer is used.

  Further, for example, carbazole-based light-emitting materials such as 4,4′-dicarbazolylbiphenyl and 1,3-dicarbazolylbenzene used in the light-emitting layer, (di) azacarbazoles, 1,3,5- Examples thereof include low-molecular light-emitting materials typified by pyrene-based light-emitting materials such as tripyrenylbenzene, polymer light-emitting materials typified by polyphenylene vinylenes, polyfluorenes, polyvinyl carbazoles, and the like. Of these, a low molecular weight light emitting material having a molecular weight of 10,000 or less is preferably used as the light emitting material.

  In the light emitting layer, the light emitting material may preferably contain about 0.1 to 20% by mass of a dopant. Examples of the dopant include known fluorescent dyes such as perylene derivatives and pyrene derivatives, phosphorescent dyes, For example, ortho-metalated iridium complexes represented by tris (2-phenylpyridine) iridium, bis (2-phenylpyridine) (acetylacetonato) iridium, bis (2,4-difluorophenylpyridine) (picolinato) iridium, and the like And complex compounds.

  Examples of the electron injection / transport layer material include metal complex compounds such as 8-hydroxyquinolinate lithium and bis (8-hydroxyquinolinate) zinc, and nitrogen-containing five-membered ring derivatives listed below. That is, oxazole, thiazole, oxadiazole, thiadiazole or triazole derivatives are preferred. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1 -Phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5-bis ( 1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1 , 3,4-thiadiazole, 1,4-bis [2- (5-phenyl) Asiazolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4 -Triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like.

  As the organic compound material used for these light emitting layers and each functional layer, a material having a polymerization reactive group such as a vinyl group in the molecule is used, and a cross-linked / polymerized film is formed after film formation to form each functional layer. May be.

  Incidentally, as the conductive material used for the anode layer, those having a work function larger than 4 eV are suitable, and metal oxides such as silver, gold, platinum, palladium and their alloys, tin oxide, indium oxide, ITO, etc. Furthermore, organic conductive resins such as polythiophene and polypyrrole are used.

  Further, as the conductive material used for the cathode layer, those having a work function smaller than 4 eV are suitable, such as magnesium and aluminum. Typical examples of the alloy include magnesium / silver and lithium / aluminum.

  Each functional layer described above is formed on the substrate and sealed with a sealing member to constitute an organic EL panel.

  Each functional layer may be formed by a vacuum method, a dry method such as a sputtering method, or may be formed by a wet method such as coating or printing.

  Next, although an organic photoelectric conversion element is demonstrated, it is not limited to the following forms.

<< Organic photoelectric conversion element >>
There is no restriction | limiting in particular as an organic photoelectric conversion element which can be used by this invention, If it is an element which has an anode and a cathode and at least 1 or more photoelectric conversion layer pinched | interposed between both and generates an electric current when irradiated with light Good.

  The configuration of the photoelectric conversion layer is not particularly limited as long as it is a configuration in which an organic semiconductor material is stacked. For example, a heterojunction type in which a p-type semiconductor material and an n-type semiconductor material are stacked, or both a p-type and an n-type semiconductor are used. A so-called bulk heterojunction type in which materials are mixed and have a microphase separation structure can be given. From the viewpoint of improving internal quantum efficiency, a configuration excellent in charge separation efficiency is preferable, and a bulk heterojunction structure is more preferable in the present application.

  In addition, when the organic photoelectric conversion element of the present invention is used as a solar cell, it is preferable to use an organic semiconductor material having an absorption characteristic optimal for the sunlight spectrum, and an organic material having a blacker appearance from the viewpoint of efficiency and designability. A photoelectric conversion element is preferable.

<< Configuration of organic photoelectric conversion element >>
In the organic photoelectric conversion element to which the present invention is applied, a transparent electrode, a photoelectric conversion layer, and a counter electrode are sequentially laminated on one surface of a support.

  In addition, the present invention is not limited thereto, and for example, a hole transport layer, an electron transport layer, a hole block layer, an electron block layer, an electrode buffer layer, a smoothing layer, or the like between the transparent electrode or the counter electrode and the photoelectric conversion layer. The organic photoelectric conversion element may be configured with the above layer. Further, it may be an electron transport layer having a hole blocking ability or a hole transport layer having an electron blocking ability. Among these, in an organic photoelectric conversion element having a bulk heterojunction type photoelectric conversion layer, a hole transport layer and / or an electron block layer are provided between the photoelectric conversion layer and the anode (usually the transparent electrode side), By forming an electron transport layer and / or a hole blocking layer between the conversion layer and the cathode (usually the counter electrode side), the charges generated in the bulk heterojunction photoelectric conversion layer can be taken out more efficiently. Therefore, it is preferable to have these layers.

  As the organic materials such as the hole transport layer and the electron transport layer, the same materials as those used in the organic EL element can be used.

(I) Anode / hole transport layer / electron block layer / photoelectric conversion layer / hole block layer / electron transport layer / cathode (ii) Anode / hole transport layer having electron blocking ability / photoelectric conversion layer / hole block Electron transport layer / cathode buffer layer / cathode (iii) anode / anode buffer layer / hole transport layer / electron block layer / photoelectric conversion layer / hole block layer / electron transport layer / cathode (iv) anode / anode Buffer layer / Hole transport layer / Electron block layer / Photoelectric conversion layer / Hole block layer / Electron transport layer / Cathode buffer layer / cathode As described above, the organic photoelectric conversion elements are stacked on the substrate by overlapping each layer. Composed. Also in the organic photoelectric conversion element, each functional layer can be formed by various known methods such as a vacuum deposition method, a dry method such as a sputtering method, and a wet method such as a coating method and a printing method.

  Also in the organic photoelectric conversion element described above, each functional layer is formed on the substrate and sealed with a sealing member to constitute an organic electronics panel.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1
<< Production of Organic EL Panel 101 (Invention) >>
<Production of gas barrier flexible film>
As a flexible film, an atmospheric pressure plasma discharge treatment apparatus having a structure described in Japanese Patent Application Laid-Open No. 2004-68143 is formed on the entire surface of a polyethylene naphthalate film having a thickness of 100 μm (a film made by Teijin DuPont, hereinafter abbreviated as PEN). Is used to form an inorganic gas barrier film (thickness 500 nm) made of SiOx, oxygen permeability is 0.001 cm ³ / (m ² · 24 h · atm) or less, water vapor permeability is 0.001 g / (m ² · 24 h) The following gas barrier flexible films were prepared.

<Formation of first electrode layer>
A 120 nm thick ITO (indium tin oxide) film was formed on the prepared gas barrier flexible film by sputtering and patterned by photolithography to form a first electrode layer. The pattern was a pattern having a light emitting area of 50 mm square and including an extraction electrode portion.

<Formation of hole transport layer>
On the first electrode layer of the gas barrier flexible film on which the prepared first electrode layer is formed, the following hole transport layer forming coating solution is applied by an extrusion coater, and then dried to form holes. A transport layer was formed. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

Before applying the hole transport layer forming coating solution, the cleaning surface modification treatment of the gas barrier flexible film is performed using a low pressure mercury lamp with a wavelength of 184.9 nm, irradiation intensity of 15 mW / cm ² , distance of 10 mm. It carried out in. The charge removal treatment was performed using a static eliminator with weak X-rays.

(Application conditions)
The coating process was performed in the atmosphere at 25 ° C. and a relative humidity of 50%.

(Preparation of coating solution for hole transport layer formation)
A solution obtained by diluting a conductive polymer PEDOT / PSS (poly (3,4-ethylenedithiothione) -poly (styrenesulphonate)) (Baytron P4083, manufactured by HC Starck) with pure water at 65% and methanol at 5%. It was prepared as a coating liquid for forming a hole transport layer.

(Drying and heat treatment conditions)
After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment. The back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.

<Formation of light emitting layer>
Subsequently, on the hole transport layer of the gas barrier flexible film formed up to the hole transport layer, the following white light emitting layer forming coating solution was applied by an extrusion coater, and then dried to form the light emitting layer. Formed. The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.

(Preparation of white light emitting layer forming coating solution)
The host material HA is 1.0 g, the dopant material DA is 100 mg, the dopant material DB is 0.2 mg, the dopant material DC is 0.2 mg, and dissolved in 100 g of toluene to form a white light emitting layer. It was prepared as a coating solution.

(Application conditions)
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, a coating temperature of 25 ° C., and a coating speed of 1 m / min.

(Drying and heat treatment conditions)
After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film forming surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., followed by a temperature of 130 ° C. A heat treatment was performed to form a light emitting layer.

<Formation of electron transport layer>
Subsequently, after forming the light emitting layer, the following coating liquid for forming an electron transport layer was applied by an extrusion coater and then dried to form an electron transport layer. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.

(Application conditions)
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.

(Coating liquid for electron transport layer formation)
The electron transport layer was prepared by dissolving EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating solution for forming an electron transport layer.

(Drying and heat treatment conditions)
After applying the coating solution for forming the electron transport layer, the solvent is removed at a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 60 ° C. Then, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.

(Formation of electron injection layer)
Subsequently, an electron injection layer was formed on the formed electron transport layer. First, the substrate was put into a decompression chamber and decompressed to 5 × 10 −4 Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.

(Formation of second electrode)
Subsequently, as a second electrode forming material under a vacuum of 5 × 10 −4 Pa on the formed electron injection layer, except for the portion that becomes the extraction electrode on the first electrode on the formed electron injection layer. Using aluminum, a mask pattern was formed by vapor deposition so as to have an extraction electrode so that the emission area was 50 mm square, and a second electrode having a thickness of 100 nm was laminated.

(Cutting)
The gas barrier flexible film formed up to the second electrode was moved again to the nitrogen atmosphere.

  The gas barrier flexible film was cut into a prescribed size to produce an organic EL device.

(Electrode lead connection)
An anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd. was used for the produced organic EL element, and a flexible printed circuit board (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12.5 μm, surface Treated NiAu plating).

  Crimping conditions: temperature 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), pressure 2 MPa, 10 seconds The electrode lead of the anisotropic conductive film and (flexible printed circuit board) on the substrate electrode lead-out part It was heated and pressurized under these conditions from the stacked electrode lead side so as to be in the form as shown in (a).

(Sealing)
A sealing member was bonded to the organic EL element to which the electrode lead (flexible printed circuit board) was connected using a commercially available roll laminating apparatus, and the organic EL panel 101 was manufactured.

  In addition, as a sealing member, a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.), a polyethylene terephthalate (PET) film (12 μm thick) with an adhesive for dry lamination (two-component reaction type urethane adhesive). The laminate used (adhesive layer thickness 1.5 μm) was used.

  A thermosetting adhesive was uniformly applied to the aluminum surface with a thickness of 20 μm along the adhesive surface (shiny surface) of the aluminum foil using a dispenser.

  The following epoxy adhesives were used as the thermosetting adhesive.

Bisphenol A diglycidyl ether (DGEBA)
Dicyandiamide (DICY)
Epoxy adduct-based curing accelerator After that, the sealing substrate is closely attached and arranged so that the take-out electrode and the electrode lead joint are covered, so that the form as shown in FIG. It was used to seal tightly, with a thick deposition condition, a pressure roll temperature of 120 ° C., a pressure of 0.5 MPa, and an apparatus speed of 0.3 m / min (FIG. 5A).

<Production of Organic EL Panel 102 (Invention)>
An organic EL element was produced in the same manner as in the production of 101, and electrode leads were connected. However, the organic EL panel 102 was manufactured by sealing so as to be in the form of FIG. The size of the substrate or the sealing member was made small so that the connection portion between the electrode lead and the electrode lead-out portion was just covered.

<Production of Organic EL Panel 103 (Comparative Example)>
An organic EL element was produced in the same manner as in the production of 101, and electrode leads were connected. However, as shown in FIG. 5C, a sealing member (glass) provided with a 0.5 mm depression in the center by sandblasting a glass plate (1 mm thick) shaped as shown in FIG. Then, the electrode lead was sandwiched between the sealing member 5 and the electrode lead portion 2a for sealing. The adhesive was cured by pressure bonding under the same conditions using the same thermal adhesive as described above.

<< Evaluation of organic EL panel >>
These panels prepared above were stored at 60 ° C. and 90% RH for 300 hours and compared with the state before storage.

(Spot evaluation method)
A current of 1 mA / cm ² was applied to the sample to emit light, and a part of the panel was magnified with a 100 × microscope (Mortex Co., Ltd. MS-804, lens MP-ZE25-200), and photographing was performed. The photographed image was cut out in a 2 mm square and visually observed to examine the situation of black spots.

A: No degradation is observed from 0 to 300 hours B: Slight degradation is observed from 0 to 300 hours C: Degradation is observed from 0 to 300 hours, but there is no practical problem D: From 0 hours to 300 hours, a level with significant deterioration and practical problems (peeling test)
An electrode lead peel test was performed using a commercially available push-pull gauge. The organic EL panel was fixed, and as shown in FIG. 8, the electrode lead was peeled off to an angle of 90 degrees, and the static peel strength at that time was measured with a push-pull gauge 10. A comparison was made between 0 hour and 300 hours. The ratio between the peel strength after storage at 60 ° C. and 90% RH for 300 hours and the peel strength before storage in%.

(Drive voltage (0 hour))
Immediately after the creation, a current of 3 mA / cm ² was passed through DC voltage / current source / monitor R6243 manufactured by ADC Co., Ltd., and the voltage was measured. The relative values are shown in the table, assuming that the voltage of the organic EL panel 101 is 100%.

(Driving voltage change with time)
A DC current and a current source / monitor R6243 manufactured by ADC Co., Ltd. were used to flow a current of 3 mA / cm ² and the voltage at that time was measured. The 0 hour value and the 300 hour value were measured.

Example 2
Organic EL panels 201 to 208 were prepared in the same manner as the organic EL panel 101. However, in Example 1, the adhesive / curing temperature of the conductive adhesive and the adhesive were changed as shown in Table 2 to prepare.

  As the ACF, the same Sony Chemical & Information Device Corporation DP3232S9 as in Example 1 was used. The pressure bonding conditions were the same as in Example 1, and only the pressure bonding temperature was performed according to the temperature described in Table 2. Panels 207 and 208 were also heated from the substrate side.

  Also, the one using a silver paste as an adhesive uses Dotite FEA-685 manufactured by Fujikura Kasei Co., Ltd. as a silver paste, and after applying the silver paste (adhesive) to ITO using a dispenser, the electrode lead is 0.05 MPa. And then bonded by heating in an oven for 15 minutes at the temperature shown in Table 2.

  The adhesion conditions of the electrode lead by the conductive adhesive of each panel are shown below.

  The manufactured organic EL panels 201 to 208 were stored at 60 ° C. and 90% RH for 300 hours, and the change in characteristics before and after that was examined in the same manner as in the example. All changes in the peel test drive voltage with time were shown as relative values with the time being 0 hours, i.e., 100 immediately after production.

  Among them, the conductive adhesive having a heating temperature of 140 ° C. or lower, or the one heated from the substrate side (that is, the one heated from both sides of the joint) is preferable.

Example 3
Next, organic EL panels 301 to 307 were prepared in the same manner as the organic EL panel 207. However, the conductive adhesive was vacuum-dried (changes the vacuum drying time), and the electrode lead was heated and dried (changed in time) in a nitrogen atmosphere, and adjusted to the conditions shown in the table.

  The electrode lead (flexible printed circuit board) was connected and connected under the same crimping conditions as in Example 1 (jig temperature 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), pressure 2 MPa, 10 seconds). . For sealing, as in Example 1, a sealing member was bonded under the same conditions using a commercially available roll laminator. Table 4 shows the moisture content of the conductive adhesive and the moisture content of the electrode lead. About an electrode lead, it is the moisture content of the polyimide film which is a base film of a flexible printed circuit board substantially.

  The water content was measured for each of the conductive adhesive and the electrode lead using a gas chromatograph mass spectrometer (6890GC / 5973MSD manufactured by Agilent Technologies).

  Each moisture content is shown below.

  The manufactured organic EL panels 301 to 307 were stored at 60 ° C. and 90% RH for 500 hours, and the change in characteristics before and after that was examined. The situation of black spots, peel test and drive voltage aging were evaluated in the same manner as in Example 1 except that the samples were stored for 500 hours. The results are shown in Table 5.

  It can be seen that the conductive adhesive and electrode lead may have a water content of 100 ppm or less.

Example 4
<< Creation of Organic Photoelectric Conversion Panel SP-401 (Invention) >>
<Production of gas barrier flexible film>
As a flexible film, an atmospheric pressure plasma discharge treatment apparatus having a structure described in Japanese Patent Application Laid-Open No. 2004-68143 is formed on the entire surface of a polyethylene naphthalate film having a thickness of 100 μm (a film made by Teijin DuPont, hereinafter abbreviated as PEN). Is used to continuously form an inorganic gas barrier film (thickness 500 nm) made of SiOx on a flexible film, with an oxygen permeability of 0.001 cm ³ / (m ² · 24 h · atm) or less, and a water vapor permeability. A gas barrier flexible film of 0.001 g / (m ² · 24 h) or less was produced.

<Formation of first electrode layer>
A 120 nm thick ITO (indium tin oxide) film was formed on the prepared gas barrier flexible film by sputtering and patterned by photolithography to form a first electrode layer. The pattern was such that the light emission area was 50 mm square.

<Formation of hole transport layer>
Before applying the hole transport layer forming coating solution, the cleaning surface modification treatment of the gas barrier flexible film is performed using a low pressure mercury lamp with a wavelength of 184.9 nm, irradiation intensity of 15 mW / cm ² , distance of 10 mm. It carried out in. The charge removal treatment was performed using a static eliminator with weak X-rays.

  Next, PEDOT / PSS (poly (3,4-ethylenedioxythiophene) -poly (polyethylene) is a conductive polymer on the first electrode layer of the gas barrier flexible film on which the prepared first electrode layer is formed. (Styrenesulfate)) (Baytron P4083, manufactured by HC Starck) was applied to a dry film thickness of 30 nm, and then dried by heating at 130 ° C. The coating process was performed in the atmosphere at 25 ° C. and a relative humidity of 50%.

<Formation of photoelectric conversion layer>
After this, the substrate was brought into the glove box and worked under a nitrogen atmosphere. First, the substrate was heat-treated at 140 ° C. for 3 minutes in a nitrogen atmosphere.

  Next, P3HT (manufactured by Plextronics: regioregular poly-3-hexylthiophene) (Mw = 52000, high-molecular p-type semiconductor material) and PCBM (Mw = 911, low-molecular n-type semiconductor) are used as the coating liquid for the photoelectric conversion layer. Material) (Frontier carbon: 6,6-phenyl-C61-butyric acid methyl ester) was mixed at a ratio of 1: 1 so as to be 3.0% by mass, and the film thickness was 150 nm while being filtered with a filter. After the coating was performed, the solvent was removed at a height of 100 mm toward the film forming surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., followed by heat treatment at a temperature of 130 ° C. A photoelectric conversion layer was formed.

<Formation of electron transport layer>
Weigh 10 mg of E-B and prepare a solution dissolved in 0.5 ml of a mixed solvent of TFPO (2,2,3,3-tetrafluoro-1-propanol): butanol = 1: 1 to a film thickness of 20 nm. Application was performed as described above, and drying was performed to form an electron transport layer.

(Application conditions)
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.

(Drying and heat treatment conditions)
After applying the coating solution for forming the electron transport layer, the solvent is removed at a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 60 ° C. Then, heat treatment was performed at a temperature of 180 ° C. to form an electron transport layer.

(Formation of second electrode)
Subsequently, as a second electrode forming material under a vacuum of 5 × 10 −4 Pa on the formed electron injection layer, except for the portion that becomes the extraction electrode on the first electrode on the formed electron injection layer. Using aluminum, a mask pattern was formed by vapor deposition so as to have an extraction electrode so that the emission area was 50 mm square, and a second electrode having a thickness of 100 nm was laminated.

(Cutting)
The gas barrier flexible film formed up to the second electrode was moved again to the nitrogen atmosphere.

  The gas barrier flexible film was cut into a prescribed size to produce an organic photoelectric conversion element.

(Electrode lead connection)
An electrode lead (polyimide film (12.5 μm) with rolled copper foil (12.5 μm)) was connected to the produced organic photoelectric conversion element using an anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd.

  Crimping conditions: temperature 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), pressure 2 MPa, 10 seconds, heated and pressurized under these conditions from the electrode lead side and bonded. At this time, the pressure bonding was performed so as to have a form as shown in FIG.

(Sealing)
A sealing member was bonded to the organic EL element to which the electrode lead was connected using a commercially available roll laminating apparatus to produce an organic photoelectric conversion panel SP-401.

  In addition, as a sealing member, a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.), a polyethylene terephthalate (PET) film (12 μm thick) with an adhesive for dry lamination (two-component reaction type urethane adhesive). The laminate used (adhesive layer thickness 1.5 μm) was used.

  A thermosetting adhesive was uniformly applied to the aluminum surface with a thickness of 20 μm along the adhesive surface (shiny surface) of the aluminum foil using a dispenser.

  The following epoxy adhesives were used as the thermosetting adhesive.

Bisphenol A diglycidyl ether (DGEBA)
Dicyandiamide (DICY)
Epoxy adduct-based curing accelerator After that, the sealing substrate is closely attached and arranged so that the take-out electrode and the electrode lead joint are covered, so that the form as shown in FIG. It was used to seal tightly, with a thick deposition condition, a pressure roll temperature of 120 ° C., a pressure of 0.5 MPa, and an apparatus speed of 0.3 m / min (FIG. 5A).

<< Creation of Organic Photoelectric Conversion Panel SP-402 (Invention) >>
The organic photoelectric conversion element was produced similarly to preparation of SP-401, and the electrode lead was connected. However, it sealed so that it might become a form of FIG.5 (b), and produced organic photoelectric conversion panel SP-402. The size of the substrate or the sealing member was made small so that the connection portion between the electrode lead and the electrode lead-out portion was just covered.

<< Creation of Organic Photoelectric Conversion Panel SP-403 (Comparative Example) >>
An organic photoelectric conversion element was prepared in the same manner as SP-401, and electrode leads were connected. However, as shown in FIG. 5C, a sealing member (glass) provided with a 0.5 mm depression in the center by sandblasting a glass plate (1 mm thick) shaped as shown in FIG. Then, the electrode lead was sandwiched between the sealing member 5 and the electrode lead portion 2a for sealing. The adhesive was cured by pressure bonding under the same conditions using the same thermal adhesive as described above.

<< Evaluation of organic photoelectric conversion panel >>
These panels prepared above were stored at 60 ° C. and 90% RH for 300 hours and compared with the state before storage.

(Retention rate of photoelectric conversion efficiency)
About the produced organic photoelectric conversion panel, the light of 100 mW / cm ² intensity of a solar simulator (AM1.5G filter) is irradiated, the IV characteristic is measured, and the retention rate (%) is calculated for each light receiving part according to the following formula 1. did.

(Formula 1)
Retention rate (%) = 60 ° C. and 90% RH short-circuit current density after storage over time / short-circuit current density before storage over time × 100
(Peel test)
An electrode lead peel test was performed using a commercially available push-pull gauge. The organic photoelectric conversion panel is fixed, and as shown in FIG. 8, the electrode lead is peeled off to an angle of 90 degrees, and the electrode lead is peeled off to an angle of 90 degrees with the push-pull gauge 10, The static peel strength was measured. Comparison was made between 0 hour (before storage with time) and 300 hours. The ratio between the peel strength after storage at 60 ° C. and 90% RH for 300 hours and the peel strength before storage in%.

  The produced organic photoelectric conversion panels SP-401 to SP-403 were stored at 60 ° C. and 90% RH for 300 hours, and changes in characteristics before and after the storage were examined. According to the method of the present invention, both the retention rate and the peel test result are good, and the organic photoelectric conversion panel shows a good sealing performance like the organic EL panel.

DESCRIPTION OF SYMBOLS 1 Resin substrate 1 'Support substrate 2 Anode 3 Organic compound layer 4 Cathode 5 Sealing member 6 Sealing adhesive 7 Electrode lead 8 Conductive adhesive

Claims (11)

An organic electronics element having a structure in which an organic compound layer including a functional layer made of at least an organic compound is sandwiched between a pair of electrodes on a support substrate, and a sealing member covering the organic electronics element between the support substrate and An organic electronics panel sandwiched between an electrode and an organic compound layer and closely sealed,
The joint between the electrode lead-out portion and the electrode lead connected to the external drive circuit is in the close-sealed region covered by the sealing member, and the electrode lead extends from the close-sealed region. Taken out,
The organic electronics panel has a pair of electrodes and a functional layer made of at least an organic compound therebetween in one direction on the support substrate in a plan view. ) A region where the one electrode and the functional layer made of the organic compound overlap, (3) a region where the one electrode and the functional layer made of the organic compound overlap the other electrode, and (4) a functional layer made of the organic compound. And the region where the other electrode overlaps, (5) the region where only the other electrode is disposed,
In addition, the joint between the electrode lead-out portion and the electrode lead connected to the external drive circuit is in the same direction as the arrangement of the regions (1) to (5), and (1) and (5) Located on the outside,
Organic electronics panel characterized by that.   2. The organic electronics panel according to claim 1, wherein the functional layer is a light emitting layer, and the organic electronics element is an organic electroluminescence element.   2. The organic electronics panel according to claim 1, wherein the functional layer is a photoelectric conversion layer, and the organic electronics element is an organic photoelectric conversion element.   The organic electronics panel according to claim 1, wherein the support substrate is a flexible resin substrate. An organic electronic element having a structure in which an organic compound layer including a functional layer made of at least an organic compound is sandwiched between a pair of electrodes on a supporting substrate, and the electrode and the organic compound between the supporting substrate by a sealing member A method for producing an organic electronics panel in which layers are sandwiched and closely sealed,
A joint portion between the electrode lead-out portion and an electrode lead connected to an external drive circuit is adhered by a conductive adhesive, and the sealing member covers the joint portion and tightly seals the organic electronics element. Stop,
The organic electronics panel has a pair of electrodes and a functional layer made of at least an organic compound therebetween in one direction on the support substrate in a plan view. ) A region where the one electrode and the functional layer made of the organic compound overlap, (3) a region where the one electrode and the functional layer made of the organic compound overlap the other electrode, and (4) a functional layer made of the organic compound. And the region where the other electrode overlaps, (5) the region where only the other electrode is disposed,
In addition, the joint between the electrode lead-out portion and the electrode lead connected to the external drive circuit is in the same direction as the arrangement of the regions (1) to (5), and (1) and (5) Located on the outside,
A method for producing an organic electronics panel.   6. The method of manufacturing an organic electronics panel according to claim 5, wherein the functional layer is a light emitting layer, and the organic electronics element is an organic electroluminescence element.   6. The method of manufacturing an organic electronics panel according to claim 5, wherein the functional layer is a photoelectric conversion layer and the organic electronics element is an organic photoelectric conversion element.   The method for manufacturing an organic electronics panel according to claim 5, wherein the support substrate is a flexible resin substrate.   6. The method of manufacturing an organic electronics panel according to claim 5, wherein a temperature at the time of adhesion of the conductive adhesive is 140 ° C. or less.   6. The method of manufacturing an organic electronics panel according to claim 5, wherein heating is performed from both sides of the joint portion when the conductive adhesive is bonded. It is a manufacturing method of the organic electronics panel according to claim 5,
A method for producing an organic electronics panel, wherein the conductive adhesive has a moisture content of 100 ppm or less, and the electrode lead has a moisture content of 100 ppm or less.

Images